Sulphonated water-soluble dyestuffs of the diamino-diphenyl series and process of preparing the same



Patented Oct; 28, 1930' UNITED STATES- PATENT "sews;

'KARL' THIESS Ann n nn'nnnnn nnrcxn, OF'HOGHST=ON,-THE-MAIN,1GERMANYL'AS- sienons T GENERAL ANILINE worms, nd, on NEW Yonx, N. Y., A CORPORATION or DELAWARE SULPHONATED WATER-SOLUBLE DYESTUFFS on THE DiAMiN -DIP'HENYL SERIES AND PROCESS on PREPARING THE, SAME No Drawing.- Applicatihnfiled February 10, 1928, Serial No. 253,584, and in Germany February 18, 1927.

Our present invention relates to new watersoluble dyestuffs and process of making them.

NHr-CalilgECaHl-NHQI wherein the hydrogen atoms of the phenyl groups may be substituted or not, suchas for instance 'benzidine, dichlorbenzid'i'ne, diphenyline (2A-diaminodiphenyl), can be condensed in both amino groups with a compound of the general formula: 7

Blg-aWl-SMOX wherein Hlg stands for an exchangeable halogen atom, R for a niti'ogroup or hydrogen and X for hydrogen or a'metal, andthat the yellow to brownish-red condensation products thus obtained are valuable dye-' stuffs.

red tints.

w Similar dyestuiis" are obtained according to the process described in German patent specification N 0. 22268 by sulfurizing the corresponding nitram'ines' They are, however,

not identical with the dyestufis' obtainable according to our present invention which have over the known dyestuffs the advantages of being 'more'l'lomogeneous and faster to light and of giving purer shades.

The condensation can be efiected in water in an open vessel at a temperature of about 100 C. or in an autoclave at a temperature up to aboutQOO C. with the addition of an acid-binding agent such as sodium carbonate, .lsodiumracetate or th'e l'il're and gives a very good toquantitive yield. In; some" cases the 7 reaction can be accelerated by'the addition of organic solvents, as-for instance alcohol,

there may also be added a"catal yst such as copper powder or the like as it is common j practice in reactions where halogen is to be heatedrto'95"v foriabout 8 hours, while stir- They are soluble in; water and dye the animal fiber greenish-yellow to'brownish- 7 ring, in a solution of 64.1 parts (=2 mole) of potassium l-chloro-2.6dinitrobenzene-4csu-l-phonate with the additionof 12 parts of calcined sodiumcarbonate in 100 parts of water. The dyestuff partly separates already in the heat; on cooling, the Whole solution of the reaction solidifies into a brownish-red paste. The d-yestufi forms when dried it brownish-red powder. It dyes wool orange tints.

The dyestu'fi? has the following formula: I

v i 7 NO} i I I V 1 102. I (2) 1 mol of diphenyline (2;4 -d'iarninodiphenyl) and 2 mols of 1-cl1'lor0-2.6-dinitrobenzene-l-sulfonic acid yield a dyestufl which sogn (3) 1 mol of-d'ianisidine '(4lxl-dia1nino- 3.3-dimethoxydiphenyl) and 2 mols of 1- chloro-2.6 dinitrobenzene-l-sulphonate yield a dyestufi which is distiin-guished by its good levelling power and dyes reddish-brown tints. It has the formula:

(4L) 1 mol of dianisidine (4.4-dian1in0- 3.3-dimethoX-ydiphenyl) and 2 mols of lchloro-2.4-dinitrobenzene 6 sulfonic acid give a dyestuif which likewise has a good levelling power and dyes reddish-brown tints. The dyestuil. has the formula:

N02 (E0133 pong iyoz I .l S0311 S0311 v 1 mol of nitrobenzidine (L F-diaminodyes golden-yellow tints. It has the follow- I Lil 2-nitrodiphenyl) and 2 mols of 1-chloro-2.6- dinitrobenzene-4-sulfonic acid yield a dyestufi dyeing orange tints. It has the formula '(6) By condensing 1 mol of benzidine in the usual manner with 2 mols of 1-chloro-2- nitrobenzene-4-sulfonic acid, a dyestufi is obtained which dyes wool a yellowish-brown tint. It has the formula:

NO: NO:

I (7) By substituting for the benzidine used inExample 6 1 mol of dianisidine (4.4-diamino-3.3-dimethoxydiphenyl), a dyestufil' is obtained dyeing reddish-brown tints. It has the following structural formula:

OCH; OCH:

WHQNHCGNH SM NO: IL'O;

(8) From 1 mol of nitrobenzidine (4. 1- diamino-2-nitrodiphenyl) and 2 mols of 1- chloro-2-nitrobenzene-4 sulfonic acid a dyestufl is obtained which dyes a brownish-yellow tint and is particularly distinguished by its excellent levelling power. The dyestufi' has the following structural formula:

SOaHQNH-GONHOSMH (9) 184 parts of benzidine, 560 parts of potassium 1-chlor0-2-nitrobenzene-4-sulphonate, 120 parts of calcined sodium carbonate and 4000 parts of water are heated in an auotoclave provided with a stirrer for 12 'hours to 120 C. to 130 C. During this operation the pressure rises to about 6 atmospheres. On cooling the dyestuif is obtained in the form of light-red needles which when redissolved and dried form a reddish-brown powder. The dyestuif' has the following structural formula:

NO: NO:

It is sparingly soluble in cold water, readily soluble in hot water to a brownish-red solution. In concentrated sulfuric acid it dissolves to a bluish-red solution which on heating turns to wine-red. The dyestufl' dyes wool from an acid bath a yellowish-brown tint.

(10) In a bomb provided with a stirrer, 244 parts of orthodianisidine are heated together with 560 parts of potassium l-chloro- 2-nitrobenzene-4-sulphonate, 120 parts of calcined sodium carbonate and 4000 parts of water for 12 hours to 120 C. to 130 C. The pressure rises to about 6 atmospheres. After cooling the dyestuff is obtained in the form of brownish-red needles which in a dry state are a brown powder. The dyestufl has the following structural formula:

OCH: OCH:

soagmiOcyN-flg NO: NO:

It is readilysoluble in hot water, sparingly soluble in cold water to a brownish-red solution. In concentrated sulfuric acid it dissolves to an intense blue solution. On heating the color of this solution is trans formed into violet. The dyestuff dyes wool from an acid bath a reddish-brown tint.

We claim:

1. The process of preparing water-soluble dyestuffs which consists in condensing a diaminodiphenyl of the following formula: NI'I2C6H4C6H4NH2 wherein the hydrogen atoms of the phenyl groups may be substituted or not, in both amino groups with a compound, of the following formula:

R NO:

Big

R NO:

wherein Hlg represents a halogen atom; R stands for a substituent of the group consisting of hydrogen, N0 SO OH and SO O-metal and R stands for a substituent of the group consisting of N0 SO OH and SO O-metal, either R or R being SO OH or SO O-metaI.

3. The process of preparing water-soluble dyestuffs which consists in condensing a diaminodiphenyl of the following formula: NH C H C6H ,NH wherein the hydrogen atoms of the phenyl groups may be substituted or not, in both aminogroups in the presence of an acid-binding agent with a compound of the following formula:

UNOz

S OaO metal 5 wherein Hlg standsforahalogen atom and R stands for the nitro group or hydrogen.

4, The process of preparing water-soluble dyestuffs which consists in condensing a diaminodiphenyl of the following formula: NH C H C I-I NH wherein the hydrogen atoms of the phenyl groups may be substituted or not, in both amino groups in the presence of an acid-binding agent with a compound of the following formula:

7. The process of preparing water soluble dyestuffs which consists in condensing a diaminodiphenyl of the following fori'nulaz 0on3 0cm NH 7 -NH:

in both amino groups in the presence of an ac1d-bind1ng agent with a compound of the following formula: 7

ONO:

I S'OzO metal p 8. The process of preparing water-soluble dyestuffs which consists in condensing a diaminodiphenyl of the following formula:

0on3 0on3 in both amino groups in the presence of an i acid-binding agent and of water at a temper- 7 S010 metal 5. The process of preparing water-soluble dyestufis which consists in condensing a diaminodiphenyl of the following formula:

I 00133 (|)C a NB NBl in both amino groups in the presence of an acid-binding agent with a compound of the following formula:

RUNOz wherein Hlg represents a halogen atom; R stands for a substituent of the group con.- sisting of hydrogen, N0 SO O'H and SO O-metal; and R stands for a substituent of the group consisting of N0 SO OH and SO O-metal, either R or R being SO OH or sO O-metal.

6. The process of preparing water-soluble dyestuffs which consists in condensing a diaminodiphenyl of the following formula:

OCH; (X111 ON H2 in both amino groups in the presence ofian N'Hg i acid-binding agent with a'cornpound ofthe following formula:

Hlg

l SO20 metal wherein Hlg stands for a halogen atom and R stands for the nitro group or hydrogen.

ature between C. and 200 C; with a compound ofthe following formula:

wherein Hlg represents a halogen atom; R

stands for a substituent of the group consisting of hydrogen, N0 SO OH and SO O-metal; and R stands for a substituent of the group consisting of N0 SO O'H and SO O-metal, either R or R being 30- 611 or SOZO-metalr c 9. The process of preparing water-soluble dyestuffs which consists in condensing-a diaminodiphenyl of the following formula:

0on3 porn 0 in both amino groups inthe presence of an acid-binding agent and of water at a temperature between 90 (land 200 C. with a compound of the following formula:

solo metal NH NH:

in both amino groups in the presence of an acid-binding agent andof water at a terns perature between 90 C. and 200 C. with a compound of the following formula:

SO1OmeLa1 11. The process of preparing a water-soluble dyestuli which consists in heating 1 mol of ortho-diamisidine of the following formula 1 m OCH:

NH NH,

in a pressure vessel provided with a stirrer together with 2 mols of potassium l-chloro- 2-nitrobenzene-4- sulphonate of the following formula:

$020K in the presence of water and sodium carbonate for 12 hours to 120 C. to 130 C.

12. As new products, the compounds of the following formula:

R R1 H H N i N0 R. RfiNO:

solo metal SO metal wherein R stands for hydrogen or OCH and R for hydrogen or N0 the said products being yellow to brownish-red powders, soluble in water and dyeing the animal fiber greenish-yellow to brownish-red tints.

13. As a new product, the compound of the following formula:

oon, oon,

wherein R represents hydrogen or alkoxy;

R stands for a substituent of the group consisting of hydrogen, N0 SO OH and SO O-metal; R stands for a substituent of the roup consisting of N0 SO Ol-l and S0 -metal, either R or R being SO OH or so O-metal and the substituted aminophenyl residue, marked I, is attached to the diphenyl residue in the 2- or 4-position, the said products being yellow to brou nislrred powders, soluble in water and dyeing animal fiber greenish-yellow to brownish-red tints.

In testimony whereof, we afiix our signatures.

KARL THIESS. BERNHARD DEICKE.

Certificate of Correction Patent N 0. 1,780,048. Granted October 28, 1930, to

KARL THIESS ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, lines 62 to 65, in the formula for N 0 read N O page 3, lines 4 to 9, in the formula insert R; and that the said Letters Patent should be read With these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 23d day of December, A. D. 1930.

[SEAL] v M. J. MOORE, Acting 00mm sz'oner of Patents, 

